B–H⋯π: a nonclassical hydrogen bond or dispersion contact?

Fanfrlík, Jindřich; Pecina, Adam; Řezáč, Jan; Sedlák, Róbert; Hnyk, Drahomı́r; Lepšı́k, Martin; Hobza, Pavel

doi:10.1039/c7cp02762a

Cited by 32 publications

(37 citation statements)

References 47 publications

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“…For example, in case of F‐substituted DB, favorable interaction (positive ΔE values) is predicted from B3LYP functional which encounters interactions other than dispersion interaction (Table ). Thus, dispersive interaction is found to be the key component in stabilizing the complexes which is in line with the majority of literatures on the nature of B‐H b ⋯π interaction …”

Section: Nature Of the Interactionsupporting

confidence: 88%

“…Thus, interactions other than dispersion are not strong enough to stabilize the complexes to a significant extent. Recent literatures also confirmed the primary role of dispersive interaction in stabilizing the complexes formed between DB and arene . However, the secondary role of other interactions cannot be ruled out from the calculated ΔE values in some of the complexes.…”

Section: Nature Of the Interactionmentioning

confidence: 84%

“…Recently, possible application of B‐H b ⋯π interaction as carrier for boron compounds has been predicted theoretically and such interactions have been explored in the formation of stable sandwich and multidecker complexes . It is to be mentioned that, all the studies have been devoted to the interaction of H b atom with delocalized π‐electrons . However, studies on B‐H b ⋯π interaction involving localized π‐electrons have received little attention.…”

Section: Introductionmentioning

confidence: 99%

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Nonclassical B‐H_b⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Saha¹,

Sharma

Bhattacharyya

2019

Int J of Quantum Chemistry

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The study presents a quantitative estimation of B-H b Á Á Áπ interaction in diboranelocalized-π half sandwiches and sandwiches. DFT-D3 method is used for geometry optimization and estimating the stability of the complexes (in terms of stabilization energies). The diborane molecule is the source of bridging hydrogen and O 2 , C 2 H 4 , and C 2 H 2 molecules are considered as the localized π-systems. MP2 and CCSD(T) calculations are also performed to measure the stability of the chosen complexes. Results indicate that the complexes are feebly stable in gas phase with stabilization energies <5.0 kcal mol −1 . Compared to DFT-D3 functionals, MP2 calculations are found to be more suitable in predicting the stability of the complexes. Dispersive interaction is the primary mode of interaction in stabilizing the complexes. Presence of substituents either on diborane or on the considered π-systems play key role in stabilizing the complexes. Thermochemical analysis demonstrates the exothermic nature of complexation. 1 H and 13 B NMR analysis are also performed. K E Y W O R D S B-H b Á Á Áπ interaction, CCSD(T), DFT-D3, dispersion interaction, MP2, sandwich

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Section: Nature Of the Interactionsupporting

confidence: 88%

Section: Nature Of the Interactionmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

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Nonclassical B‐H_b⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Saha¹,

Sharma

Bhattacharyya

2019

Int J of Quantum Chemistry

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“…The electrostatic repulsion in these counterintuitive cases is overwhelmed by the stabilizing polarization, dispersion interaction, and most importantly, the charge transfer interaction, resulting eventually counterintuitively in an overall attraction. Similarly, the high-level ab initio and symmetry adapted perturbation theory (SAPT) [131] calculations on close B-H• • • π contacts, which have been observed in crystallographic structures of Ir-dithiolene-phosphine complexes containing a boron hydride cluster [132], have reinterpreted the nature of B-H• • • π contacts in this system. Although the characteristics of the B-H• • • π interaction have been known for decades, these authors argued that they disproved the widely-accepted view that these are attractive electrostatic interactions that arise as a consequence of the intermolecular interaction.…”

Section: Introductionmentioning

confidence: 85%

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

2019

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In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions that contribute to packing in the solid-state. It may be relatively straightforward to identify Type-II halogen bonding between atoms using the conceptual framework of σ-hole theory, especially when the interaction is linear and is formed between the axial positive region (σ-hole) on the halogen in one monomer and a negative site on a second interacting monomer. A σ-hole is an electron density deficient region on the halogen atom X opposite to the R–X covalent bond, where R is the remainder part of the molecule. However, it is not trivial to do so when secondary interactions are involved as the directionality of the interaction is significantly affected. We show, by providing some specific examples, that halogen bonds do not always follow the strict Type-II topology, and the occurrence of Type-I and -III halogen-centered contacts in crystals is very difficult to predict. In many instances, Type-I halogen-centered contacts appear simultaneously with Type-II halogen bonds. We employed the Independent Gradient Model, a recently proposed electron density approach for probing strong and weak interactions in molecular domains, to show that this is a very useful tool in unraveling the chemistry of halogen-assisted noncovalent interactions, especially in the weak bonding regime. Wherever possible, we have attempted to connect some of these results with those reported previously. Though useful for studying interactions of reasonable strength, IUPAC’s proposed “less than the sum of the van der Waals radii” criterion should not always be assumed as a necessary and sufficient feature to reveal weakly bound interactions, since in many crystals the attractive interaction happens to occur between the midpoint of a bond, or the junction region, and a positive or negative site.

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“…[12][13][14][15] Boranes and carboranes are recently targeted because of their potential to form BH � � � p interactions with the π-face of an arene. [16][17][18][19] It has been suggested that these BH � � � p interactions may be driven by a nonspecific weak dispersion contact, as for example based on restrained fit to the electrostatic potential and symmetryadapted perturbation theory studies [20,21] or molecular orbital analyses. [22] However, these approaches are not free from some arbitrariness, therefore they are generally not suited for deriving more definite conclusions on a particular bonding situation.…”

Section: Introductionmentioning

confidence: 99%

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

et al. 2019

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We report the thermodynamic stabilities and the intrinsic strengths of three‐center‐two‐electron B−B−B and B−Hb−B bonds (Hb : bridging hydrogen), and two‐center‐two‐electron B−Ht bonds (Ht : terminal hydrogen) which can be served as a new, effective tool to determine the decisive role of the intermediates of hydrogenation/dehydrogenation reactions of borohydride. The calculated heats of formation were obtained with the G4 composite method and the intrinsic strengths of B−B−B, B−Hb−B, and B−Ht bonds were derived from local stretching force constants obtained at the B3LYP‐D2/cc‐pVTZ level of theory for 21 boron‐hydrogen compounds, including 19 intermediates. The Quantum Theory of Atoms in Molecules (QTAIM) was used to deepen the inside into the nature of B−B−B, B−Hb−B, and B−Ht bonds. We found that all of the experimentally identified intermediates hindering the reversibility of the decomposition reactions are thermodynamically stable and possess strong B−B−B, B−Hb−B, and B−Ht bonds. This proves that thermodynamic data and intrinsic B−B−B, B−Hb−B, and B−Ht bond strengths form a new, effective tool to characterize new (potential) intermediates and to predict their role for the reversibility of the hydrogenation/dehydrogenation reactions.

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B–H⋯π: a nonclassical hydrogen bond or dispersion contact?

Cited by 32 publications

References 47 publications

Nonclassical B‐H_b⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Nonclassical B‐H_b⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻

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B–H⋯π: a nonclassical hydrogen bond or dispersion contact?

Cited by 32 publications

References 47 publications

Nonclassical B‐Hb⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Nonclassical B‐Hb⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

Quantitative Assessment of B−B−B, B−Hb−B, and B−Ht Bonds: From BH3 to B12H122−

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Product

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Nonclassical B‐H_b⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Nonclassical B‐H_b⋯π interaction in diborane⋯localized‐π sandwiches: A DFT‐D3 study

Quantitative Assessment of B−B−B, B−H_b−B, and B−H_t Bonds: From BH₃ to B₁₂H₁₂²⁻